WO2024253479A1 - Dispositif électroluminescent organique - Google Patents

Dispositif électroluminescent organique Download PDF

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WO2024253479A1
WO2024253479A1 PCT/KR2024/007838 KR2024007838W WO2024253479A1 WO 2024253479 A1 WO2024253479 A1 WO 2024253479A1 KR 2024007838 W KR2024007838 W KR 2024007838W WO 2024253479 A1 WO2024253479 A1 WO 2024253479A1
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mmol
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organic layer
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Korean (ko)
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김민준
홍성길
차용범
서상덕
김영석
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LG Chem Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight

Definitions

  • the present invention relates to an organic light-emitting device with improved driving voltage, efficiency, and lifespan.
  • the organic luminescence phenomenon refers to the phenomenon of converting electrical energy into light energy using organic materials.
  • Organic light-emitting devices utilizing the organic luminescence phenomenon have a wide viewing angle, excellent contrast, fast response time, and excellent brightness, driving voltage, and response speed characteristics, so much research is being conducted.
  • Organic light-emitting devices generally have a structure including an anode, a cathode, and an organic layer between the anode and the cathode.
  • the organic layer is often composed of a multilayer structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device, and may be composed of, for example, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc.
  • Patent Document 1 Korean Patent Publication No. 10-2000-0051826
  • the present invention relates to an organic light-emitting device with improved driving voltage, efficiency, and lifespan.
  • the present invention provides the following organic light-emitting device:
  • the above light-emitting layer comprises a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2.
  • Ar 1 and Ar 2 are each independently a substituted or unsubstituted C 6-60 aryl; or a C 2-60 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,
  • L 1 is a single bond; or a substituted or unsubstituted C 6-60 arylene,
  • L 2 and L 3 are each independently a single bond; a substituted or unsubstituted C 6-60 arylene; or a C 2-60 heteroarylene comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,
  • R 1 to R 7 is connected to a substituent -Ar 3 , and the others are each independently hydrogen or deuterium,
  • Ar 3 is a substituted or unsubstituted C 6-60 aryl; or a C 2-60 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,
  • Ar' 1 is hydrogen; deuterium; substituted or unsubstituted C 6-60 aryl; or C 2-60 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,
  • Ar' 2 and Ar' 3 are each independently a substituted or unsubstituted C 6-60 aryl; or a C 2-60 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,
  • L' 1 to L' 3 are each independently a single bond; a substituted or unsubstituted C 6-60 arylene; or a C 2-60 heteroarylene comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,
  • L' 4 is a single bond or a substituted or unsubstituted C 6-60 arylene
  • R' 1 is hydrogen or deuterium
  • a is an integer from 1 to 8
  • the deuterium substitution rate of the compound represented by the above chemical formula 2 is 50% or more.
  • the organic light-emitting device described above can improve efficiency, low driving voltage, and/or lifespan characteristics in the organic light-emitting device by including a compound represented by the chemical formula 1 and a compound represented by the chemical formula 2 in the light-emitting layer.
  • Figure 1 illustrates an example of an organic light-emitting device composed of a substrate (1), an anode (2), a light-emitting layer (3), and a cathode (4).
  • Figure 2 illustrates an example of an organic light-emitting device composed of a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (7), a light-emitting layer (3), a hole blocking layer (8), an electron injection and transport layer (9), and a cathode (4).
  • substituted or unsubstituted means a group which is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a nitrile group; a nitro group; a hydroxy group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; an alkylthioxy group; an arylthioxy group; an alkylsulfoxy group; an arylsulfoxy group; a silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; an aralkyl group; an aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; a heteroarylamine group; an aryl
  • the "substituent linked with two or more substituents” can be a biphenyl group. That is, the biphenyl group can be an aryl group, or it can be interpreted as a substituent in which two phenyl groups are connected.
  • the carbon number of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it can be a compound having the following structure, but is not limited thereto.
  • the ester group may have the oxygen of the ester group substituted with a straight-chain, branched-chain or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms.
  • it may be a compound having the following structural formula, but is not limited thereto.
  • the number of carbon atoms in the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
  • the silyl group specifically includes, but is not limited to, a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, etc.
  • the boron group specifically includes, but is not limited to, a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, a phenyl boron group, etc.
  • halogen groups include fluorine, chlorine, bromine or iodine.
  • the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the number of carbon atoms in the alkyl group is 1 to 20. According to another embodiment, the number of carbon atoms in the alkyl group is 1 to 10. According to another embodiment, the number of carbon atoms in the alkyl group is 1 to 6.
  • alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-e
  • the alkenyl group may be linear or branched, and the carbon number is not particularly limited, but is preferably 2 to 40. According to one embodiment, the carbon number of the alkenyl group is 2 to 20. According to another embodiment, the carbon number of the alkenyl group is 2 to 10. According to another embodiment, the carbon number of the alkenyl group is 2 to 6.
  • Specific examples include, but are not limited to, vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl, and styrenyl.
  • the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms.
  • examples thereof include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like.
  • the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms.
  • the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, or the like, but is not limited thereto.
  • the polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, or the like, but is not limited thereto.
  • the fluorenyl group may be substituted, and two substituents may be combined with each other to form a spiro structure.
  • the fluorenyl group is substituted, It can be, but is not limited to, the following.
  • a heterocyclic group is a heterocyclic group containing at least one of O, N, Si, and S as a heteroatom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms.
  • heterocyclic groups include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, carb
  • the aryl group among the aralkyl group, the aralkenyl group, the alkylaryl group, and the arylamine group is the same as the examples of the aryl group described above.
  • the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the examples of the alkyl group described above.
  • the heteroaryl among the heteroarylamine may be applied with the description of the heterocyclic group described above.
  • the alkenyl group among the aralkenyl group is the same as the examples of the alkenyl group described above.
  • the description of the aryl group described above may be applied with the exception that arylene is a divalent group.
  • the description of the heterocyclic group described above may be applied with the exception that heteroarylene is a divalent group.
  • the description of the aryl group or cycloalkyl group described above may be applied with the exception that the hydrocarbon ring is not monovalent and is formed by combining two substituents.
  • the description of the heterocyclic group described above may be applied, except that the heterocyclic group is not monovalent and is formed by combining two substituents.
  • deuterated or deuterium substituted means that at least one of the substitutable hydrogens in the compound, divalent linking group or monovalent substituent is replaced with deuterium.
  • unsubstituted or substituted with deuterium or “substituted or unsubstituted with deuterium” means “unsubstituted or substituted with 1 to 9 deuterium atoms”.
  • unsubstituted or substituted with deuterium phenanthryl can be understood to mean “unsubstituted or substituted with 1 to 9 deuterium atoms", considering that the maximum number of hydrogen atoms that can be substituted with deuterium in the phenanthryl structure is 9.
  • deuterated structure is meant to encompass compounds of all structures, divalent linkages or monovalent substituents in which at least one hydrogen is replaced by a deuterium.
  • deuterated structure of phenyl can be understood to refer to monovalent substituents of all structures in which at least one substitutable hydrogen in the phenyl group is replaced by a deuterium, as follows.
  • the deuterium substitution rate of a compound is calculated as a percentage of the number of substituted deuteriums compared to the total number of hydrogens that can exist in the compound (the sum of the number of hydrogens replaceable with deuterium in the compound and the number of substituted deuteriums). Therefore, the deuterium substitution rate of a compound being "K%" means that K% of the hydrogens replaceable with deuterium in the compound have been replaced with deuterium.
  • the above “deuterium substitution rate” or “deuteration degree” can be measured by a commonly known method using MALDI-TOF MS (Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometer), nuclear magnetic resonance spectroscopy (1H NMR), TLC/MS (Thin-Layer Chromatography/Mass Spectrometry), or GC/MS (Gas Chromatography/Mass Spectrometry).
  • MALDI-TOF MS Microx-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometer
  • nuclear magnetic resonance spectroscopy (1H NMR
  • TLC/MS Thin-Layer Chromatography/Mass Spectrometry
  • GC/MS Gas Chromatography/Mass Spectrometry
  • the "deuterium substitution rate” or “deuteration degree” can be obtained by obtaining the number of substituted deuteriums in the compound through MALDI-TOF MS analysis, and then calculating the ratio of the number of substituted deuteriums to the total number of hydrogens that can exist in the compound as a percentage. Therefore, the deuterium substitution rate of a compound being "K%" means that K% of the hydrogens in the compound that can be replaced with deuterium have been replaced with deuterium.
  • the "deuterium substitution rate” or “degree of deuteration” can be obtained by calculating the substitution rate based on the maximum value (max. value) of the distribution of molecular weights at the end of the reaction.
  • the "deuterium substitution rate” or “deuteration degree” can be calculated from the integration amount of the total peak using the integration ratio on 1H NMR.
  • deuterium does not exist at a specific position means that the deuterium substitution rate at that position is 10% or less, and does not mean that the deuterium substitution rate is 0%.
  • deuterium exists at a specific position means that the deuterium substitution rate at that position is more than 1%, and does not mean that the deuterium substitution rate at that position is 100%.
  • the "deuterium substitution rate at a specific position” can be calculated by comparing the 1H NMR spectrum of a compound where deuterium is not substituted with the 1H NMR spectrum of a compound where deuterium is substituted, and confirming the rate at which the integral of each peak decreases for each hydrogen (proton) position.
  • the anode and cathode used in the present invention refer to electrodes used in organic light-emitting devices.
  • anode material a material having a high work function is generally preferred so that hole injection into the organic layer can be smooth.
  • Specific examples of the above anode material include, but are not limited to, metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO 2 :Sb; and conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline.
  • metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof
  • metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO)
  • combinations of metals and oxides such as ZnO:Al
  • the cathode material is preferably a material having a low work function to facilitate electron injection into the organic layer.
  • Specific examples of the cathode material include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayered materials such as LiF/Al or LiO 2 /Al.
  • the organic light-emitting device according to the present invention may additionally include a hole injection layer on the anode, if necessary.
  • the above hole injection layer is a layer that injects holes from the electrode
  • the hole injection material is preferably a compound that has the ability to transport holes, has an excellent hole injection effect at the anode, an excellent hole injection effect for the light-emitting layer or the light-emitting material, prevents movement of excitons generated in the light-emitting layer to the electron injection layer or the electron injection material, and has excellent thin film forming ability.
  • the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer.
  • hole injection materials include, but are not limited to, metal porphyrins, oligothiophenes, arylamine-based organic compounds, hexanitrilehexaazatriphenylene-based organic compounds, quinacridone-based organic compounds, perylene-based organic compounds, anthraquinones, and conductive polymers of polyaniline and polythiophene-based compounds.
  • the organic light-emitting device may include a hole transport layer on the anode (or on the hole injection layer when a hole injection layer is present) as needed.
  • the above hole transport layer is a layer that receives holes from the anode or the hole injection layer and transports the holes to the light-emitting layer.
  • a hole transport material that can transport holes from the anode or the hole injection layer and transfer them to the light-emitting layer is suitable, and a material with high mobility for holes is suitable.
  • hole transport materials include, but are not limited to, arylamine-based organic compounds, conductive polymers, and block copolymers having both conjugated and non-conjugated portions.
  • the above electron blocking layer is a layer placed between the hole transport layer and the light emitting layer to prevent electrons injected from the cathode from being recombined in the light emitting layer and from passing to the hole transport layer. It is also called an electron suppression layer or electron blocking layer. A material having a lower electron affinity than the electron transport layer is preferable for the electron blocking layer.
  • the light-emitting layer used in the present invention refers to a layer that can emit light in the visible light range by combining holes and electrons transferred from the anode and the cathode.
  • the light-emitting layer includes a host material and a dopant material, and in the present invention, the compound represented by the chemical formula 1 and the compound represented by the chemical formula 2 are included as hosts.
  • the compound represented by the chemical formula 1 may be represented by any one of the following chemical formulas 1-1 to 1-3:
  • Ar 1 to Ar 3 , L 1 to L 3 and R 1 to R 7 are as defined in chemical formula 1.
  • Ar 1 and Ar 2 can each independently be a substituted or unsubstituted C 6-20 aryl; or a C 2-20 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,
  • Ar 1 and Ar 2 can each independently be phenyl, biphenylyl, terphenylyl, triphenylsilyl phenyl, naphthyl, phenanthrenyl, dibenzofuranyl, or dibenzothiophenyl, wherein phenyl, biphenylyl, terphenylyl, triphenylsilyl phenyl, naphthyl, phenanthrenyl, dibenzofuranyl, and dibenzothiophenyl can independently be unsubstituted or substituted with one or more deuterium atoms.
  • Ar 1 and Ar 2 may each independently be any one selected from the group consisting of: wherein Ar 1 and Ar 2 may each independently be unsubstituted or substituted with one or more deuterium atoms:
  • L 1 is a single bond; or it may be a substituted or unsubstituted C 6-20 arylene,
  • L 1 may be a single bond, a substituted or unsubstituted phenylene, or a substituted or unsubstituted naphthalenediyl,
  • L 1 can be a single bond, phenylene, or naphthalenediyl, wherein each of the phenylene and naphthalenediyl can be independently unsubstituted or substituted with one or more deuterium atoms.
  • L 2 and L 3 can each independently be a single bond; or a substituted or unsubstituted C 6-20 arylene; or a C 2-20 heteroarylene comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,
  • L 2 and L 3 may each independently be a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenyldiyl, or a substituted or unsubstituted naphthalenediyl,
  • L 2 and L 3 may each independently be a single bond, phenylene, biphenyldiyl, or naphthalenediyl, wherein the phenylene, biphenyldiyl and naphthalenediyl may each independently be unsubstituted or substituted with one or more deuterium atoms.
  • L 2 and L 3 may each independently be a single bond or one selected from the group consisting of: wherein L 2 and L 3 may each independently be unsubstituted or substituted with one or more deuterium atoms:
  • Ar 3 may be, independently, hydrogen; deuterium; substituted or unsubstituted C 6-20 aryl; or C 2-20 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,
  • Ar 3 can be phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, naphthyl phenyl, phenyl naphthyl, fluoranthenyl, dihydroindenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, or benzonaphthothiophenyl, wherein phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, naphthyl phenyl, phenyl naphthyl, fluoranthenyl, dihydroindenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, and benzonaphthothiophenyl can be unsubstituted or substituted with
  • At least one of Ar 1 to Ar 3 may be naphthyl, phenyl naphthyl, naphthyl phenyl, phenanthrenyl, fluoranthenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, or benzonaphthothiophenyl, wherein each of the naphthyl, phenyl naphthyl, naphthyl phenyl, phenanthrenyl, fluoranthenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, and benzonaphthothiophenyl may independently be unsubstituted or substituted with one or more deuterium atoms.
  • At least one of Ar 1 to Ar 3 may be naphthyl, phenyl naphthyl, naphthyl phenyl, fluoranthenyl, dibenzofuranyl, benzonaphthofuranyl, or benzonaphthothiophenyl, wherein each of the naphthyl, phenyl naphthyl, naphthyl phenyl, fluoranthenyl, dibenzofuranyl, benzonaphthofuranyl and benzonaphthothiophenyl may independently be unsubstituted or substituted with one or more deuterium atoms.
  • Dn means that n hydrogens are replaced with deuterium
  • n is an integer greater than or equal to 13
  • Ar 1 to Ar 3d , L 1d to L 3d and R 1d to R 7d represent Ar 1 to Ar 3 , L 1 to L 3 and R 1 to R 7 substituents which are not substituted with deuterium, respectively.
  • n of Dn may be 13 or more, 14 or more, 15 or more, 16 or more, 17 or more, 18 or more, or 19 or more, and 50 or less, 45 or less, 40 or less, 38 or less, 36 or less, 34 or less, 32 or less, 30 or less, 28 or less, 26 or less, 24 or less, 23 or less, 22 or less, 21 or less, or 20 or less.
  • the compound represented by the above chemical formula 1 can be manufactured, for example, by a manufacturing method such as the following reaction scheme 1, or by additionally performing a deuterium substitution reaction after performing reaction scheme 1, and the remaining compounds can also be manufactured similarly.
  • Ar 1 , Ar 2 , L 1 to L 3 and R 1 to R 7 are as defined in the above chemical formula 1, X 1 is halogen, and preferably X 1 is chloro or bromo.
  • the above reaction scheme 1 is a Suzuki coupling reaction, which is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be changed as known in the art.
  • the above-described deuterium substitution reaction is preferably performed in the presence of D 2 O, and the reactor, catalyst, solvent, etc. for the deuterium substitution reaction can be changed as appropriate for the desired product as known in the art.
  • the above manufacturing method can be more specifically described in the manufacturing example described below.
  • the meaning of 'phenanthrenyl is substituted with at least one deuterium' means 'at least one of the nine carbons on which deuterium of the phenanthrenyl of the chemical formula 2 can be substituted has a deuterium, not hydrogen.
  • the deuterium substitution rate at each carbon of the phenanthrenyl can be obtained by comparing the 1 H NMR spectrum of a compound on which deuterium is not substituted with the 1 H NMR spectrum of a compound on which deuterium is substituted, as described above.
  • the chemical formula 2 can be represented by any one of the following chemical formulas 2A to 2I.
  • a' is an integer from 0 to 7
  • Ar' 1 to Ar' 3 , L' 1 to L' 4 and R' 1 are as defined in the chemical formula 2.
  • Ar' 1 may be a C 2-20 heteroaryl comprising at least one selected from the group consisting of hydrogen; deuterium; substituted or unsubstituted C 6-20 aryl; or substituted or unsubstituted N, O and S,
  • Ar' 1 can be hydrogen; deuterium; or substituted or unsubstituted C 6-20 aryl.
  • Ar' 1 can be hydrogen; deuterium; or phenyl which is unsubstituted or substituted with one or more deuterium atoms.
  • Ar' 1 may be hydrogen; or deuterium.
  • Ar' 2 and Ar' 3 can each independently be a substituted or unsubstituted C 6-20 aryl; or a C 2-20 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,
  • Ar' 2 and Ar' 3 may each independently be phenyl, biphenylyl, terphenylyl, quarterphenylyl, naphthyl, phenyl naphthyl, naphthyl phenyl, tetrahydronaphthyl, phenanthrenyl, phenyl phenanthrenyl, triphenylenyl, dimethylfluorenyl, diphenylfluorenyl, carbazolyl, phenyl carbazolyl, dibenzofuranyl, dibenzothiophenyl, or phenyl dibenzofuranyl, and said phenyl, biphenylyl, terphenylyl, quarterphenylyl, naphthyl, phenyl naphthyl, naphthyl phenyl, tetrahydronaphthyl, phenanthrenyl, phenyl phenanthrenyl, triphenylenyl,
  • Ar' 2 and Ar' 3 are each independently phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenyl naphthyl, naphthyl phenyl, tetrahydronaphthyl, phenanthrenyl, phenyl phenanthrenyl, triphenylenyl, dimethylfluorenyl, diphenylfluorenyl, carbazolyl, phenyl carbazolyl, dibenzofuranyl, dibenzothiophenyl, phenyl dibenzofuranyl, tetramethyl tetrahydronaphthyl, methyl phenyl, isopropyl phenyl, tertbutyl phenyl, ditertbutyl phenyl, methyl biphenylyl, isopropyl biphenylyl, tertbutyl biphenylyl, dimethyl biphenyly
  • Ar' 2 and Ar' 3 can each independently be phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, tetrahydronaphthyl, tetramethyltetrahydronaphthyl, phenyl substituted with one or two methyl groups, phenyl substituted with one or two isopropyl groups, phenyl substituted with one or two tertbutyl groups, dibenzofuranyl, or dibenzothiophenyl, wherein said phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, tetrahydronaphthyl, tetramethyltetrahydronaphthyl, phenyl substituted with one or two methyl groups, phenyl substituted with one or two isopropyl groups, phenyl substituted with one or two tertbutyl groups,
  • L' 1 to L' 3 may each independently be a single bond; a substituted or unsubstituted C 6-20 arylene; or a C 2-20 heteroarylene comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,
  • L' 1 to L' 3 may each independently be a single bond, phenylene, biphenylylene, naphthylene, phenyl naphthylene, phenanthrenylene, carbazolylene, phenyl carbazolylene, dibenzofuranylene, phenyl dibenzofuranylene, or dimethylfluorenylene, and wherein phenylene, biphenylylene, naphthylene, phenyl naphthylene, phenanthrenylene, carbazolylene, phenyl carbazolylene, dibenzofuranylene, phenyl dibenzofuranylene, and dimethylfluorenylene may each independently be unsubstituted or substituted with one or more deuterium atoms.
  • L' 1 is a single bond
  • L' 2 and L' 3 can each independently be a single bond; a substituted or unsubstituted C 6-20 arylene; or a C 2-20 heteroarylene comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,
  • L' 1 is a single bond
  • L' 2 and L' 3 can each independently be a single bond, phenylene, biphenylylene, naphthylene, phenyl naphthylene, phenanthrenylene, carbazolylene, phenyl carbazolylene, dibenzofuranylene, phenyl dibenzofuranylene, or dimethylfluorenylene, and wherein phenylene, biphenylylene, naphthylene, phenyl naphthylene, phenanthrenylene, carbazolylene, phenyl carbazolylene, dibenzofuranylene, phenyl dibenzofuranylene, and dimethylfluorenylene can each independently be unsubstituted or substituted with one or more deuterium.
  • L' 1 is a single bond
  • L' 2 and L' 3 can each independently be a single bond, phenylene, biphenylylene, naphthylene, or phenyl naphthylene, wherein the phenylene, biphenylylene, naphthylene and phenyl naphthylene can each independently be unsubstituted or substituted with one or more deuterium atoms.
  • L' 4 may be a single bond or a substituted or unsubstituted C 6-20 arylene
  • L' 4 may be a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylylene, or a substituted or unsubstituted naphthylene,
  • L' 4 may be a single bond, phenylene, biphenylylene or naphthylene, wherein each of the phenylene, biphenylylene and naphthylene may independently be unsubstituted or substituted with one or more deuterium atoms.
  • the compound represented by chemical formula 2 can be represented by the following chemical formula 2-1:
  • Ar' 1 to Ar' 3 , L' 1 to L' 3 , R' 1 and a are as defined in the chemical formula 2 above,
  • R' 2 is hydrogen; deuterium; or substituted or unsubstituted C 6-60 aryl,
  • b is an integer from 0 to 4.
  • R' 2 may be hydrogen; deuterium; or substituted or unsubstituted C 6-20 aryl,
  • R' 2 can be hydrogen, deuterium, or phenyl which is unsubstituted or substituted with deuterium.
  • the deuterium substitution rate of the compound represented by the above chemical formula 2 may be 50% to 100%. Specifically, the deuterium substitution rate of the compound may be 50% or more, 60% or more, 70% or more, 75% or more, 80% or more, or 90% or more, but less than or equal to 100%.
  • the compound represented by the above chemical formula 2 may contain, but is not limited to, 16 to 50 deuterium atoms. More specifically, the compound may contain 16 or more, 17 or more, 18 or more, or 19 or more, and 50 or less, 45 or less, 40 or less, 38 or less, 36 or less, 34 or less, 32 or less, 30 or less, 28 or less, 26 or less, 24 or less, 23 or less, 22 or less, 21 or less, or 20 or less deuterium atoms.
  • Dn means that the total number of substituted deuterium (D) in the entire compound is n
  • n is a value including a
  • Ar' 1d to Ar' 3d and L' 1d to L' 4d represent Ar' 1 to Ar' 3 and L' 1 to L' 4 substituents which are not substituted with deuterium, respectively,
  • -At least one of -L' 1d -Ar' 1d and R' 1 is deuterium.
  • n is the total number of deuteriums substituted in the compound, which is an integer that makes the deuterium substitution rate of the compound 50% or more, and is a value that includes a or a+1, which is the number of deuteriums substituted on phenanthrenyl.
  • the compound represented by the chemical formula 2-D means a compound in which phenanthrenyl is substituted with a or a+1 deuteriums and the entire compound is substituted with n deuteriums. The reason why the number of deuteriums substituted on phenanthrenyl is a or a+1 is because -L' 1d -Ar' 1d can be deuterium.
  • n of Dn may be 16 or more, 17 or more, 18 or more, or 19 or more, and 50 or less, 45 or less, 40 or less, 38 or less, 36 or less, 34 or less, 32 or less, 30 or less, 28 or less, 26 or less, 24 or less, 23 or less, 22 or less, 21 or less, or 20 or less.
  • D is deuterium
  • n1 is an integer from 1 to 9
  • n is the total number of deuterium atoms substituted in the compound
  • Each of the above compounds has a deuterium substitution rate of 50% or more.
  • the compound represented by the above chemical formula 2 can be manufactured by a manufacturing method as in the following reaction scheme 2, for example, if it is a compound represented by the above chemical formula 2-D, and the remaining compounds can also be manufactured similarly.
  • the compound represented by chemical formula 2 is prepared by subjecting each deuterium-substituted reactant to a Suzuki coupling reaction.
  • the deuterium substitution reaction (step 1) is followed by the Suzuki coupling reaction (step 2).
  • the deuterium substitution reaction is preferably carried out in the presence of D 2 O, and the reactor, catalyst, solvent, etc. for the deuterium substitution reaction can be changed to suit the desired product as known in the art.
  • the Suzuki coupling reaction is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be changed as known in the art.
  • the above manufacturing method can be further specified in the manufacturing examples described below.
  • the weight ratio of the compound represented by the chemical formula 1 and the compound represented by the chemical formula 2 in the light-emitting layer is 10:90 to 90:10, and more preferably 20:80 to 80:20, 30:70 to 70:30 or 40:60 to 60:40.
  • the light-emitting layer may additionally include a dopant in addition to the host.
  • the dopant material is not particularly limited as long as it is a material used in an organic light-emitting device.
  • the dopant may include an aromatic amine derivative, a styrylamine compound, a boron complex, a fluoranthene compound, a metal complex, etc.
  • the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, periflanthene, etc.
  • the styrylamine compound is a compound in which at least one arylvinyl group is substituted in a substituted or unsubstituted arylamine, and one or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group are substituted or unsubstituted.
  • the dopant may include, but is not limited to, styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc.
  • the metal complex may include, but is not limited to, an iridium complex, a platinum complex, etc.
  • the dopant material may be one or more compounds selected from the group consisting of, but is not limited to:
  • the above hole-blocking layer is a layer placed between the electron transport layer and the light-emitting layer to prevent holes injected from the anode from being recombined in the light-emitting layer and from passing to the electron transport layer. It is also called a hole suppression layer or hole blocking layer. A material with high ionization energy is preferable for the hole-blocking layer.
  • the organic light-emitting device may include an electron transport layer on the light-emitting layer, if necessary.
  • the above electron transport layer is a layer that receives electrons from the cathode or the electron injection layer formed on the cathode and transports the electrons to the light-emitting layer, and also suppresses the transfer of holes from the light-emitting layer.
  • the electron transport material a material that can well receive electrons from the cathode and transfer them to the light-emitting layer, and a material with high electron mobility is suitable.
  • the electron transport material include, but are not limited to, Al complexes of 8-hydroxyquinoline; complexes containing Alq 3 ; organic radical compounds; hydroxyflavone-metal complexes, etc.
  • the electron transport layer can be used with any desired cathode material as has been used in the prior art.
  • suitable cathode materials are conventional materials having a low work function followed by an aluminum layer or a silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.
  • the organic light-emitting device may additionally include an electron injection layer on the light-emitting layer (or on the electron transport layer when an electron transport layer is present), if necessary.
  • the above electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an excellent electron injection effect for an electron injection effect from a cathode, a light-emitting layer or a light-emitting material, prevents movement of excitons generated in the light-emitting layer to the hole injection layer, and it is preferable to use a compound having excellent thin film forming ability.
  • materials that can be used as the electron injection layer include, but are not limited to, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, and their derivatives, metal complex compounds, and nitrogen-containing five-membered ring derivatives.
  • 8-hydroxyquinolinato lithium bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h]quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)(o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, Bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc., but are not limited thereto.
  • the "electron injection and transport layer” is a layer that performs the roles of both the electron injection layer and the electron transport layer, and materials performing the roles of each layer may be used alone or in combination, but are not limited thereto.
  • FIGS. 1 and 2 illustrate the structure of an organic light-emitting device according to the present invention.
  • FIG. 1 illustrates an example of an organic light-emitting device composed of a substrate (1), an anode (2), a light-emitting layer (3), and a cathode (4).
  • FIG. 2 illustrates an example of an organic light-emitting device composed of a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (7), a light-emitting layer (3), a hole blocking layer (8), an electron injection and transport layer (9), and a cathode (4).
  • the organic light-emitting device according to the present invention can be manufactured by sequentially stacking the above-described configurations.
  • a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation is used to deposit a metal or a conductive metal oxide or an alloy thereof on a substrate to form an anode, and then each of the above-described layers is formed thereon, and then a material that can be used as a cathode is deposited thereon, thereby manufacturing the device.
  • the organic light-emitting device can be manufactured by sequentially depositing a cathode material on a substrate in the reverse order of the above-described configurations to an anode material (WO 2003/012890).
  • the light-emitting layer can be formed by a host and a dopant not only by a vacuum deposition method but also by a solution coating method.
  • the solution coating method means, but is not limited to, spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc.
  • the organic light-emitting device may be a front-emitting type, a back-emitting type, or a double-sided emitting type depending on the material used.

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  • Materials Engineering (AREA)
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  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne un dispositif électroluminescent organique ayant une tension de commande, une efficacité et une durée de vie améliorées.
PCT/KR2024/007838 2023-06-08 2024-06-10 Dispositif électroluminescent organique Pending WO2024253479A1 (fr)

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KR1020240074506A KR20240174511A (ko) 2023-06-08 2024-06-07 유기 발광 소자
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200129334A (ko) * 2019-05-08 2020-11-18 덕산네오룩스 주식회사 유기전기 소자용 화합물을 포함하는 유기전기소자 및 그 전자 장치
KR20210114892A (ko) * 2020-03-11 2021-09-24 주식회사 엘지화학 유기 발광 소자
KR20220092362A (ko) * 2020-12-24 2022-07-01 엘티소재주식회사 헤테로고리 화합물, 이를 포함하는 유기 발광 소자, 이의 제조 방법 및 유기물층용 조성물
KR20220147538A (ko) * 2021-04-27 2022-11-03 주식회사 엘지화학 유기 발광 소자
KR20230069868A (ko) * 2021-11-12 2023-05-19 주식회사 엘지화학 유기 발광 소자

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200129334A (ko) * 2019-05-08 2020-11-18 덕산네오룩스 주식회사 유기전기 소자용 화합물을 포함하는 유기전기소자 및 그 전자 장치
KR20210114892A (ko) * 2020-03-11 2021-09-24 주식회사 엘지화학 유기 발광 소자
KR20220092362A (ko) * 2020-12-24 2022-07-01 엘티소재주식회사 헤테로고리 화합물, 이를 포함하는 유기 발광 소자, 이의 제조 방법 및 유기물층용 조성물
KR20220147538A (ko) * 2021-04-27 2022-11-03 주식회사 엘지화학 유기 발광 소자
KR20230069868A (ko) * 2021-11-12 2023-05-19 주식회사 엘지화학 유기 발광 소자

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